Certain 2-oxo-4-thiazoline-5-carboxylic acid esters

ABSTRACT

Thiazolinone-(2)-carboxylic acid esters having the formula:   ARE PREPARED BY REACTING A Beta -AMINO ACRYLIC ACID ESTER WITH CHLOROCARBOXYL SULPHENYL CHLORIDE (COCl-SCl) at a temperature of from 0 to 200*C. The esters are useful as plant protecting agents such as a fungicide.

United States Patent [1 1 Grohe et al.

[ Dec. 9, 1975 Frohberger, Leverkusen, both of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: July 12, 1972 21 Appl. No.: 271,104

[44] Published under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 271,104.

[30] Foreign Application Priority Data July 28, 1971 Germany 2137649 [52] US. Cl. 260/306.7 R; 424/270 [51] Int. Cl. C07D'277/14 [58] Field of Search 260/3067 [56] References Cited OTHER PUBLICATIONS I Cameron et al., J. Chem. Soc., 1934, pp. 1330-1332.

Elderfield (ed.), Heterocyclic Compounds, Vol. 5,

N.Y., John Wiley & Sons, 1957, pp. 496-501, 548-549, 624-625. Sunkel et al., J. Med. Chem, 1970, 334-335.

Primary Examiner-R. Gallagher Attorney, Agent, or Firm-Burgess, Dinklage & Sprung [57] ABSTRACT Thiazolinone-(2)-carboxylic acid esters having the formula:

are prepared by reacting a B-amino acrylic acid ester with chlorocarboxyl sulphenyl chloride (COCl-SCl) at a temperature of from O to 200C. The esters are useful as plant protecting agents such as a fungicide.

4 Claims,- No Drawings BACKGROUND This invention relates to a process for the production of thiazolinone-(2)carboxy1ic acid esters.

It is known that enamino esters of the B-anilino crotonic acid ester type will undergo an intermolecular reaction with S Cl to give the corresponding disulphide, but will not react by an intramolecular cyclisation to give the corresponding thiazathiole (Ann. 675, 154 (1964)).

SUMMARY It has now surprisingly been found that thiazolinone- '(2)-carboxylic esters having the following general formula:

l 2 O S COOR in which n=lor2and,wheren=l,

R represents a hydrogen atom, an optionally branched C to C -alkyl radical or a C to C cycloalkyl radical, these radicals being optionally substituted by a phenyl radical which may itself be substituted one or more times by fluorine, chlorine or bromine atoms, or by C to C -alkyl radicals; a phenyl radical optionally substituted one or more times by fluorine, chlorine or bromine atoms or by C to C -a1ky1 groups; or an optionally substituted naphthyl radical; and

where R represents applymethylene group with from 2 to 6 carbon atoms or a metaor para-phenylene group.v

R represents an optionally branched C to C -alkyl radical or a C or C -cycloalkyl radical, these radicals being optionally substituted by one or more C to C alkoxy, nitrile or alkoxy carbonyl groups or by a phenyl radical which is itself optionally substituted one or more times by fluorine, chlorine or bromine atoms or C to C -alkyl radicals; and

R may have one of the meanings listed for R or represents a hydrogen atom; a lower alkoxy carbonyl group, preferably a methoxy carbonyl or ethoxy carbonyl group; or a phenyl radical optionally substituted one or more times by fluorine, chlorine or bromino atoms, or C to C alkyl groups; or an optionally substituted naphthyl radical, can be obtained by reacting B-amino acrylic acid esters of the general formula:

in which n, R, R and R are as defined above, with chlorocarbonyl sulphenyl chloride of the formula:

DESCRIPTION The B-amino acrylic acid esters which may be used as starting materials are known and can be readily obtained by reacting acyl acetic esters with ammonia or primary amines, [Organicum, Organisch Chem. Grundpraktikum VEB Deutscher Verlag d. Wissenschaften, Berlin, page 354 (1964); J. Amer. Chem. Soc. 68, 514 (1946)], by reacting Grignard compounds with cyano acetic esters [Collection of Czechoslovak. Chemical Communications 25, 607 (1960)] or by reacting propiolic acid esters or acetylene dicarboxylic esters with ammonia or primary amines [Monatshefte f. Chemie 36, 109 (1915); Chem. Ber. 99, 2526 (1966); Nippon Kagaku Zasshi 82, 632 (1961)].

The following are preferably used in the reaction according to the inventiomfi-amino crotonic acid methyl ester, B-amino crotonic acid ethyl ester, B- amino crotonic acid-isopropyl ester, B-amino crotonic acid-n-dodecyl ester, B-amino crotonic acid benzyl e'ster, B-amino crotonicacid cyclohexyl ester, B-amino crotonic acid-B-phenethyl ester, fi-methyl amino crotonic 'acid ethyl ester, B-anilino crotonic acid ethyl ester, B-benzyl amino crotonic acid ethyl ester, B-[pchloranilino-1-crotonic acid ethyl ester,-B-amino cinnamic acid ethyl ester, B-amino-B-ethyl acrylic acid ethyl ester, B-methyl amino cinnamic acid ethyl ester, a-aminofumaric acid diethyl ester,a-anilino maleic acid diethyl ester, a-m-chloroanilino maleic acid diethyl ester, N,N -ethylene-bis-[B-amino crotonic acid ethyl ester], N,N'-p-pheny1ene-bis-[B-amino crotonic acid ethyl ester].

Chlorocarbonyl sulphenyl chloride is also known and readily accessible. It can readily be obtained by reacting trichloromethane sulphenyl chloride with concentrated sulphuric acid (Synthesis 1970, 576).

The reacton of B-amino acrylic acid esters with chlorocarbonyl sulphenyl chloride according to the invention is carried out at temperatures of from 0 to 200C, preferably from 10 to C.

In general, the B-amino acrylic acid ester and the chlorocarbonyl sulphenylchloride are heated to between 30'and 200C, preferably between 30 and 150C, in a molar ratio of from 1:1 to 1:2, desirably in an inert solvent, until the evolution of hydrogen chloride stops. In general, the reaction is complete after from 1 to 4 hours.

It is, of course, also possible to combine the hydrogen chloride liberated using one of the bases commonly employed for this purpose, for example pyridine or calcium carbonate.

Suitable'inert solvents for use in the process according to the invention include hydrocarbons or chlorinated hydrocarbons such as benzene, toluene, chlorobenzene, o-dichlorobenzene or carbon tetrachloride, tetramethylensulfon and dioxan are also examples of suitable solvents.

The process according to the invention is illustrated by w'ayof example with reference to the reaction of B-a'mino crotonic acid ethyl ester and of N,N'-ethylene-bis-[ fl-amino crotonic acid ethyl ester]with chlorocarbonyl sulphenyl chloride:

CH fi-NH CH a 0001 H 2 05 01s I k 2 H01 a c ooc o 5 [H c ooc-cmc-NH-cti 7 l 2 0001301 CH3 CH5 n-ca ca -n n c ooc s o s 0000 11 way, a large number of new thiazolinone-(2)-carboxylic acid esters having the following general formula:

I v 2 o s COOR n in which,

n= 1 or2andwheren=l R" represents an optionally branched C to C alkyl radical or C or C -cycloalkyl radical, these radicals being optionally substituted by a phenyl radical which may itself be substituted one or more times by fluorine, chlorine or bromine or by C to C -alkyl radicals; a phenyl radical optionally substituted one or more times by fluorine, chlorine or bromine atoms, or by C to C -alkyl groups; or a optionally substituted naphthyl radical; and where n 2 R" represents a polymethylene group with from 2 to 6 carbon atoms or a metaor para-phenylene group;

R represents an optionally branched C to C alkyl radical or a C or C -cycloalkyl radical, these radicals being optionally substituted by one or more C to C -alkoxy, nitrile or alkoxy carbonyl groups or by a phenyl radical which is itself optionally substituted one or more times by fluorine, chlorine or bromine atoms or, by C to C -alkyl radicals; and

R may have one of the meanings listed above for R" or represents a hydrogen atom, a lower alkoxy carbonyl group; or a phenyl radical optionally substituted one or more times by fluorine, chlorine or bromine atoms or C to C -alkyl group or an optionally substituted naphthyl radical have been made available by this process.

The thiazolinone-(2)-carboxylic acid esters of formula (IV) are also new where, if n l,

R" represents hydrogen;

R has the meaning defined above; and

R represents an alkoxy carbonyl group, preferably a methoxy carbonyl or ethoxy carbonyl group.

Particularly preferred new compounds are those of the formula (IV) in which n l; and

R" representsan optionally branched C to C alkyl radical or a phenyl radical optionally substituted by one or more fluorine, chlorine or bromine atoms or by C to C -alkyl groups;

R represents an optionally branched C to C alkyl radical, optionally substituted by a phenyl radical; and

' R has the same meaning as R' or represents a hydrogen atom; a methoxy carbonyl or ethoxy carbonyl group; or a phenyl radical.

The thiazolinone-(2)-carboxylic acid esters are valuable starting materials for the synthesis of plant-protection agents and can also be used as such directly.

Their fungicidalactivity is illustrated by way of example with reference to 4-methyl.thiazolinone-(2)-carboxylic acid (5 -isopropyl ester and 4-methyl thiazolinone-(2)-carboxylic acid-(5)-B-phenethyl ester having the formulae (V) and (Vl) respectively:

(cH cHooc CH5 o c n ca cn ooc s o I I rim and with reference to 4-methyl thiazolinone-(2)-carboxylic acid-(5)-benzyl ester, 4-methyl thiazolinone- (2)-carboxylic, acid (5)-n-butyl ester and 4-methyl thiazolinone-(2)-carboxylic acid-(5)-cyclohexyl ester which have all been found to have good activity in EXAMPLE heated to ll30C for a further 1 to 2 hours, after 10 which it is worked up either by fractional distillation or by recrystallisation.

Some of the thiazolinone-(2)-carboxylic esters obby fluorine, chlorine or bromine atoms or by C, to C -alkyl groups; 1

R is selected from the group of C to C -alk,yl or [C +C C to C -alkyl substituted by phenyl which is itself optionally substituted one or more times by fluorine, chlorine or bromine atoms or by C to C -alkyl; and

R is the same as R or is selected from the group of hydrogen, methoxy carbonyl, ethoxy carbonyl and phenyl which is itself optionally substituted one or more times by fluorine, chlorine or bromine atoms or by C to C -alkyl.

2. Thiazolinone-(Z)-carboxylic acid esters of claim 1 tained in this way are shown in the following Table: wherein R" is hydrogen and R is C to C alkoxy Thiazoli one- 2 -carbo lie esters of the e era].

formula I n 12' n 12 mp. (c) or Yield (96 or b JTorr theoretical) OH C H CH 62 82 0 11 03 0 :1 (:11 197 199/o.5 66

H C H CH 178 H (CH 0H CH '1 56 6O 1 H (2 3 011 011 CH 141 55 'l G H CH CH 159 78 l H 11 12 25 5 1 (3 H C 3 COOC H 56 58 74 2 -CH CH CH CH 209 1 H C H CH CH 70 1 H -0 13 on 96 78 1 H an 151 65 H CH CH 212 40 l H CH CO1 128 60 What is claimed is: 1. Thiazolinone-(2)-carboxylic acid esters of the formula:

R1. l I

wherein R" is selected from the group of C to C -alkyl, phenyl, and phenyl substituted one or more times carbonyl.

3. Thiazolinone-(2)-carboxylic acid esters of claim 1 wherein R" is selected from the group of methyl benzyl, phenyl, 2,6-dichlorophenyl; and

R is selected from the group of methyl and ethyl;

and

R is selected from the group of methyl and ethoxycarbonyl.

4. Thiazolinone-(2)-carboxylic acid esters of claim 3 selected from the following 3 ,4-dimethyl-thiazolinone-( 2 )-carboxylic ethylester,

acid-( 5 

1. THIAZOLINONE-(2)-CARBOXYLIC ACID ESTERS OF THE FORMULA:
 2. Thiazolinone-(2)-carboxylic acid esters of claim 1 wherein R1 is hydrogen and R3 is C1 to C3 alkoxy carbonyl.
 3. Thiazolinone-(2)-carboxylic acid esters of claim 1 wherein R1 is selected from the group of methyl benzyl, phenyl, 2,6-dichlorophenyl; and R2 is selected from the group of methyl and ethyl; and R3 is selected from the group of methyl and ethoxycarbonyl.
 4. Thiazolinone-(2)-carboxylic acid esters of claim 3 selected from the following 3,4-dimethyl-thiazolinone-(2)-carboxylic acid-(5)-ethylester, 4-methyl-3-benzyl-thiazolinone-(2)-carboxylic acid-(5)-ethylester, 4-methyl-3-phenyl-thiazolinone-(2)-carboxylic acid-(5)-ethylester, 4-methyl-3-phenyl-thiazolinone-(2)-carboxylic acid-(5)-methylester, 4-methyl-3-(2'',6''-dichlorophenyl)-thiazolinone-(2)-carboxylic acid-(5)-ethylester, 3-phenyl-4-ethoxy carbonyl-thiazolinone-(2)-carboxylic acid-(5)-ethylester. 